Insoluble azo dye containing aromatic nucleus of the diphenyl series



Patented Mar. 12, 1940 A UNITE SATES INSOLUBLE AZO DYE CONTAINING ARO- MATIC NUOLEUS OF SERIES THE DIPHENYL H Miles Augustinus Dahlen and I Newell' Meade Bigelow, Wilmington, and Frithjof Zwilgrneyer, Arden, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., acorporation of 7 Delaware No Drawing. Application February 3, 1937, I

Serial No. 123,860 y 13 Claims. (Cl. 260-193) This invention relates to new compounds, to new compositions of matter, to processes of dyeing andto processes of making the new compounds. Moreparticularly the invention relates to new compositions of matter including azo dyes, and

p to processes of employing them, particularly in printing processes. The invention will be described with reference to particular examples:

which are illustrative but not limitative thereof. 3 The azo dyes are a well-defined group containing the chromophor -N=N'. The chromogen of azo dyestuffs comprises two aryl radicals with the chromophor between them. The mono azo dyes are generally prepared by joining two com- 1 phenol, an amine, or an active methylene compound, is called the'coupling component. In coupling the components, the azo component is diazotized, and is reacted with thesecond component, usually in solution. The azo dyes of the prior art are dyed by different processes depending on the nature and'properties of the particular dyes. When the completed dyestufi is substantive to the material to be dyed the dye is disposed in a suitable liquid medium and the material' -is dipped therein. When the coupling component or the diazotized azo componentof the dye is substantive to the ['3 material to be dyed, the substantive component can be afiixed to the material and the other component can be coupled therewith to complete the dye on the material. Thisinvention relates to compounds and to processes of making the compounds which are applied to the material and formed by still another process, according to which an 9.20 component is diazotized and coupled to a compound with which it forms a new.

compound stable in alkaline or neutral medium, do and is mixed with the coupling component of the dye and with the other ingredients of a basic or neutral printing paste, or solution; rial to be dyed is impregnated with the paste, or with the solution, by printing or in any other satisfactory manner and the dye is formed on the material by reaction with an acid, whereby it is freed and enabled to react with the coupling component. I

In copending application Serial No. 55,410 filed December 20, 1935, Patent No. 2,115,412 dated ponents 01': which the first, an amine, is called the azo component, and the second, usually a The mate- April 26, 1938 of which this application isa continuation-in-part which are formed by coupling a-diazotized arylamine represented by the formula 1" in which Z isone of a group consisting of hydrofgen, amino and an naauxochrome' hereinafterito be defined, X is one of agroupconsisting of hydrogen and n-auxochroma-and a. is aninteger, I

at least two less thanthe number of carbon atoms compounds -were disclosed I in aryl, with a compoundrepresented by :the

in which Y is one of a group consisting of hydro- I genand an n'-'auxochrome, bis' an integer at Y least 2 less than the number of carbon atoms" in aryl', R1 is one of a group consisting of hydrogen, alkyl, aryl, and aralkyl, R2 is one of a group consisting of alkyl, aryl, aralkylfand acyl' and R1 and R2 may be nuclear elements of one hetero- 5 diazotizedarylamines capable ofcoupling with diazo salts.- Another object of the invention is to prepare the new compounds and new compositions of matter-ofthisinvention by methods which areeconomically and technically satisfactory. Anotherobject of the invention is to produce materials dyed in satisfactory shades of yellow. Other objects of the invention will be in part apparent and in part more fully hereinafter set forth.

The major .objectfloi the invention is accomplished generally by dyeing dye-susceptible materials with compounds formed by coupling a diazotized arylamine'which was herein'before described with a coupling component represented by the formula in which aryl is a residue of a diphenyl compound, b is an integer at least four less than the number of carbon atoms in aryl and Y is representative of the groups and values already given in the above general formula. Another object of the invention is attained by stabilizing a diazotized arylamine of the said formula against reaction in non-acid medium, and incorporating it in a non-acid medium with an aceto-acetylarylamine of the said formula. Another object of the invention is attained by impregnating a dye-susceptible material with one of the said new compositions of matter and exposing it to the action of acid fumes. Another object of the invention is accomplished by preparing the new compounds and compositions of matter by technically and economically satisfactory methods, the details of certain of which are more fully hereinafter set forth.

In the practice of the invention the azo componentis stabilized against reaction in alkaline or neutral medium with acoupling component either by forming the nitrosamine or a diazoimino compound thereof, of which both methods will be understood by persons skilled in the art. The stabilized azo component will then be mixed in the form of dry powder, a paste, or a solution with the alkaline or neutral mass containing the coupling component. The details of the processes of practicing the invention will differ somewhat according to the state of the ingredients but the general method is to impregnate the colorable material with the so-formed mixture, and to act upon it with enough acid to regenerate the azo component and permit it to act upon the coupling component.

In the form of the invention which involves the dyeing of a cloth by the so-called process of printing, the azo component, diazotized and stabilized as hereinabove described, is mixed in a basic paste with the coupling component, the paste is applied to an etched or printing roller which impregnates the fabric by contact, the fabric is placed in a closed container, and is subjected for a few seconds, at elevated temperature and usually in the presence of water vapor, to the action of the fumes of an acid which neutralizes the basicity of the paste, breaks up the stabilized complex, and frees the azo component for reaction with the coupling component.

The aryl components of the new dyestuffs may advantageously include as nuclear substituents one or more of the n-auxochromes, which in the diphenyl compound may be substituted in either or both benzene rings. The n-auxochromes we define to consist of the group alkyl, alkoxy, aryl, aralkyl, aralkoxy, aryloxy, hydro-aryl, hydroaryloxy, nitro, halogen, and trifluoromethyl. Generally speaking, satisfactory results are obtained by the use of azo components having from 0 to 3 of such substituents and the use of larger number of n-auxochrome substituents does not appear to produce results advantageous enough towarrant the extra expense of incorporating them. It is also possible to incorporate in the aryl nuclei water-solubilizing substituents such as the carboxylic and sulfonic acid groups, but such incorporation tends to water-solubilize colors and make them useless for ordinary dyeing purposes. Consequently, such substituents will be used only in those comparatively rare instances when a water-soluble color is desired.

Illustrative of the general utility as azo components of primary arylamines are the following:

Ortho-chloro-aniline 2:5-dich1oro-aniline 4--chloro-2-amino-pheneto1 Ortho-anisidine 4-chloro-2 5-dimethyl-aniline 4-benzoylamino-2 5 -dimethoxyaniline 5-nitro-2-amino-anisole l -methoxy-2-naphthylamine 4-chloro-2-amino-diphenyl-ether Meta-amino-benzo-trifluoride Ortho-amino -azo-toluene 4 4' -diamino -diphenylamine 3-amino-carbazole Sarcosin 1-methyl-amino-ethane-2-sulfonic-acid Proline Nipecotinic-acid Benzylene-imine-para-sulfonic-acid l-naphthylamine-Z 4 8-trisulfonic-acid Z-ethyl-amino-4-sulfo-benzoic-acid Examples of other derivatives of diazotized arylamines which are inactive toward coupling components under alkaline conditions, but which revert to the diazo form when reacted upon by acids, are for instance the so-called azo-sulfonates, compounds having the formula i The following examples, in which parts are by weight, are designed to illustrate but not to limit the various features of the invention:

Example I A printing paste was prepared according to the following formula:

2.5 parts of acetoacet-acetyl-tolidine prepared from acetyl-tolidine by aceto-acetylation in xylene at about 150 C. in the usual manner, 0 the following probable formula (l t H O a white product having a melting point of 221 C.

2.5 parts of the diazoimino compound of the formula /CH2CH2 CH GH3 G1 I C O ONa obtained by the action of diazotized 4-chloro-2- amino-anisole on alpha-piperidine-carboxylicacid.

27.0 parts water 3. 0 parts sodium hydroxide solution of 35% strength.

65.0parts of starch-tragacauth thickener of the following composition:

100. 0 parts Y 80 parts wheat starch 360 parts gum tragacanth6% solution 560 parts water 1000 parts Cotton piece goods were printed from an engraved roll with the above paste, the prints dried in the air, and then subjected to the action of live steam containing the vapors of acetic acid.

Color development took place and the printed goods were rinsed with water, boiled for 5 minutes in an 0.5% soap solution, again rinsed, and

dried. A bright yellow dyeing appeared. The' new color had the probable formula:

CH3 CH3 Example II 2.5 parts of acetoacet-acetyl-tolidine as mentioned in Example I. 2.5 parts of the diazoimino compound of the formula obtained by the action of diazotiz ed 4-chloro-2- amino-toluene on methyl-glucamine, was developed in a similar manner as in Example I to a bright greenish yellow of the probable formula Example III 2.6 parts of 'acetoacet-acetyl-tolidine as mentioned in Example I. 2.4 parts of the tetrazoimino compound of the formula CHaOH(CHOH)4-CH2lTl-N=N obtained by the action of tetrazotized tolidine on methyl-glucamine was developed in a similar manner as in Ex amplel to a bright orange of the probable formula I CH3 CH3 l I H 2 CH3 CH3 CH2, I

1 l l 0=o Y. Example IV 2.2 parts of acetoacet-acetyl-tolidine as mentioned in Example I. 2.8 parts of the .diazoimino compound of the formula GH:\ CH3 CH3 onxcnonnomon obtained by the action of the diazo of 4-amino- 4'-dimethyl-amino-azo-benzene on methyl glu- I camine was developed in a similar manner as in Examplel to a yellowish brown of the probable formula 2.4 parts of acetoacet-acetyl benzidine prepared from acetyl-benzicline by aceto-acetylation, of the probable formula v CHaCO Gino ONE-@QNEO 0 cm.

A white compound of M. P. 240 C.

2.6 parts of the diazoimino compound of the formula I I v I 00113 I r l /CH2(CHOH)4CH:OH

I on; 01

obtained by the action of diazotized4-chloro-2- amino-anisole on'methyl-glucamine was devel oped in a similar manner as in Example-I to a bright yellow of the probable formula Example VI 2.5 parts of acetoacet-acetyl-benzidine as mentioned inEXample V; 2.5 parts of the diazoimino compound as ,mentioned in. Example II was dev'elopedin a similar manner as in Example "I to-a bright greenish yellow of the probable formula onto ONE-@Q-NHCO 31100 CH3 nna N G N Example VII 2.6 parts of acetoacet-acetyl-benzidine as mentioned in Example V. 2.4 parts of the diazoimino compound as mentioned in Example III was developed in a similar manner as in Example I to a bright orange of the probable formula Similar dyes may be prepared from acetoacetacetyl-dichlorbenzidine or acetoacet-acetyl-dianisidine and diazoimino compounds of ice color bases.

The following groups are mentioned as examples of the group the residue of piperidine c1ncru and the residue of morpholine Gui-011K N o GHQ-cu:

Tetrazotized arylene-diamines may be coupled to two equivalents of coupling components to produce the compound having the 'formula in which the groups and values in the formula are the same as those hereinbefore set forth.

In the foregoing examples, the colors have been produced by the use of the diazo-components in the form of their water-soluble diazoimino derivatives, but they may also be produced by the use of the diazo salts prepared from the diazo components, by the use of the nitrosamines (anti-diazotates) and by the other methods Wellknown in the art.

The invention is applicable to the dyeing of cotton, regenerated cellulose, cellulose esters and ethers, and, with somewhat less satisfactory results, to the dyeing of wool, silk, and leather.

The examples illustrate the colors as selfshades, but they may be used in mixtures, to produce a wide range of shades. The colors also may be applied in combination with reds and blues to yield a wide range of browns and blacks.

'As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. An azo compound comprising the radical of a diazotized arylamine coupled to the radical of an acylated aceto-acetyl-diphenyl compound in which the acyl group is devoid of groups which couple with diazo salts.

2. An azo compound comprising the radical of a diazotized aryl amine which is devoid of water-solubilizing groups coupled with the radical of an aryl amide of aceto-acetic acid represented by the formula in which aryl is a radical of the diphenyl series, Y is one of a 'group consisting of hydrogen and the n-auxochromes, b is an integer at least four less than the number of carbon atoms in aryl, NR1R2 is one of a group consisting of the radical of piperidine, the radical of morpholine and amine radicals in which R1 is one of the group consisting of hydrogen, alkyl, aryl, and aralkyl and R2 is one of a group consisting of alkyl, aryl, aralkyl and acyl which is devoid of groups capable of coupling with diazo salts.

3. An azo compound comprising the radical of a diazotized arylamine coupled with an arylamide of acetoacetic acid represented by the formula in which aryl is a radical of the diphenyl series, Y is one of a group consisting of hydrogen and the n-auxochromes, b is an integer at least four less than the number of carbons in aryl, and R2 is alkyl, aryl, aralkyl and acyl which is devoid of groups capable of coupling with diazo salts.

4. A compound represented by the formula in which aryl is the radical of an arylamine compound.

til

5. A compound represented by the formula A1Y1N=N in which aryl is the radical of an arylamine compound and M is the radical of, a hydrocarbon carboxylic acid devoid of groups which couple with diazo salts. g

6. A compound represented by the formula CH3 CH3 I l ll ll H H O ArylN=N in which aryl is the radical of an arylamine compound devoid of solubilizing groups, M is the radical of a hydrocarbon carboxylic acid devoid of groups which couple with diazo salts.

'7. A compound represented by the formula CH3 CH3 [I I H o.

Ary1-N=N of an arylamine in which R1 and R2 represent nuclear carbons of a carbocyclic compound, aryl is the nucleus of in which aryl is the a diphenyl compound, and aryl is: the radical 6r an arylamine devoid of solubilizing groups.

10. A compoundrepresented by the formula:

o H 11.0 -o

, Aryl-N=N in which. aryl" is the radical of a compound of the diph enyl series, Y is one of a group consisting of hydrogen and n-auxochrome, b is an integer at least four less than the number of carbons in aryl", and aryl is the radical of an arylamine which isdevoid of solubilizing groups.

11. A compound represented by the formula:

ot otH=( 1 I'ar 1"-1I I-fi:+oo-c H3 0 H H 'oo,

. Y ArylN=N I in which aryl is the radical of a compound ofthe diphenyl series, Y'is one of a group consisting of hydrogen and n-auxochrome, bis aninteger at least four less than the number of carbons in aryl, and aryl is the radical of an arylamine which is devoid of solubilizing groups.

'12. A compound represented by the formula:

void of solubilizing groups and aryl is the radical.

of a diphenyl compound.

13. The compound represented by the formula:

7 MILES AUGUSTINUS DAI-ILEN. NEWELL MEADE BIGELOW. FRITHJOF ZWILGMEYER.

radical'of an arylamine de- 

